WO2004106252A1 - Revetement hydrophobe et/ou oleophobe pour surfaces de verre presentant des sites d'adhesion pour des materiaux d'etancheite - Google Patents

Revetement hydrophobe et/ou oleophobe pour surfaces de verre presentant des sites d'adhesion pour des materiaux d'etancheite Download PDF

Info

Publication number
WO2004106252A1
WO2004106252A1 PCT/EP2003/014768 EP0314768W WO2004106252A1 WO 2004106252 A1 WO2004106252 A1 WO 2004106252A1 EP 0314768 W EP0314768 W EP 0314768W WO 2004106252 A1 WO2004106252 A1 WO 2004106252A1
Authority
WO
WIPO (PCT)
Prior art keywords
atoms
coating
composition according
weight
composition
Prior art date
Application number
PCT/EP2003/014768
Other languages
English (en)
Inventor
Michael Overs
Gerhard Jonschker
Original Assignee
Nanogate Coating Systems Gmbh
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nanogate Coating Systems Gmbh filed Critical Nanogate Coating Systems Gmbh
Priority to AU2003298231A priority Critical patent/AU2003298231A1/en
Publication of WO2004106252A1 publication Critical patent/WO2004106252A1/fr

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/08Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/006Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • C03C17/007Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2203/00Other substrates
    • B05D2203/30Other inorganic substrates, e.g. ceramics, silicon
    • B05D2203/35Glass

Definitions

  • Hydrophobic and/or oleophobic coating for glass surfaces with adhesion sites for sealants Hydrophobic and/or oleophobic coating for glass surfaces with adhesion sites for sealants
  • This invention is related to a hydrophobic and/or oleophobic easy-to-clean coating on glass surfaces containing particles embedded in the surface of said coating such that the coating exhibits improved adhesion to a sealant.
  • Hydrophobic and/or oleophobic coatings are typically produced by treating a glass pane with some sort of fluorinated alkylsilanes to render the surface hydrophobic and/or oleophobic. Due to the low surface energy of such coatings, usual sealants do not adhere very well to this type of surfaces.
  • Common adhesion promotion coatings comprise silanes to provide improved adhesion between glass panes and sealants.
  • US 4,857,366 B teaches a method for treating a glass surface providing improved adhesion of a sealant applied thereafter using a composition comprising a silane.
  • WO 99/19084 Al teaches a water based coating material comprising an alcohol as a solvent, fluorinated silanes and an acid to provide a hydrophobic coating on glass.
  • EP 0 799 873 Bl teaches a coating material comprising water, an alcohol, fluorinated silanes and an acid to provide a hydrophobic coating in glass.
  • WO 95/23804 Al teaches a water based coating material comprising fluorinated silanes to provide a hydrophobic coating on a variety of substrates.
  • US 6,340,502 Bl teaches a coating material comprising a fluorinated alkoxysilane and a fluorinated halosilane for obtaining a hydrophobic coating.
  • EP 0 545 201 Bl teaches an article comprising a glass substrate, which is treated with a silica primer layer and a perfluoroalkyl alkyl silane.
  • EP 1 113 064 Al teaches a water based composition comprising a tetraalkoxysilane, an alkylsilane, and an acid for obtaining a hydrophobic coating.
  • DE 100 51 182 Al teaches nanoparticles that are modified with hydrocarbons, which may be fluorinated, and a process for deposition of hydrophobic coatings comprising said nanoparticles. As may be seen from the examples, it is questionable, whether nanoparticles are formed at all. In this description, no nanoparticles are added to the composition, but nanoparticles are formed in situ.
  • DE 195 44 912 Al teaches microporous polytetrafluoroethylene that is filled with nanoparticles.
  • DE 197 19 948 Al and DE 197 46 885 Al teach a process for obtaining nanostructured surfaces by applying surface modified nanoparticles onto a substrate and polymerizing the composition subsequently.
  • the problem underlying the invention is that current hydrophobic and/or oleophobic coatings for glass do not exhibit good adhesion to common sealants, and on the other hand, adhesion promotion coatings for sealants on glass do not exhibit good hydrophobicity, so far.
  • the problem of the invention is to provide a composition overcoming said contradiction. Surprisingly, it has been found that a coating on glass surfaces is achievable, which exhibits both hydrophobicity and sufficient adhesion to sealants.
  • the problem of the underlying invention is solved by a composition, comprising a. 0.01% to 10% by weight of particles with a diameter up to 100 nm, b. 0.1% to 10% by weight of at least one alkylsilane conforming to the general formula 1
  • R 1 , R 2 and R 3 each independently is chlorine or an organic residue containing 1 to 17 carbon atoms, 3 to 37 hydrogen atoms, 0 to 6 oxygen atoms, 0 to 33 fluorine atoms, 0 to 33 chlorine atoms, and 0 to 5 nitrogen atoms and
  • R 4 is an organic residue containing 1 to 17 carbon atoms, 3 to
  • the underlying problem is solved, such that the hydrophobic and/or oleophobic coating on glass is selectively rendered adhesive to sealants by incorporation of particles into the coating that function as adhesion sites to the sealant.
  • Hydrophobic according to the invention is characterized by a contact angle against water in air of > 90°. Unless otherwise stated, said contact angle is determined by dynamic advancing contact angle measurements using a Kr ⁇ ss TM instrument.
  • Fig. 1 shows that typically the embedded particles in a coating composition are covered with the hydrophobic and/or oleophobic material, in the case of the invention this is said alkylsilane. But it was found that the degree of coverage with said alkylsilanes strongly depends on the chemical nature of stabilizers in the particle dispersion and the surface modification of the particles. Very good results have been obtained by using SiO 2 particles modified with organic residues containing alcohol functional groups, ethylenic functional groups and/or amino functional groups.
  • Fig. 2 demonstrates the basic principle of the present invention.
  • the solution contains at least the solvent, particles, non-sticking compounds and sticking compounds or compounds with sticking and non-sticking moieties.
  • the solvent evaporates and the particles migrate to the inner sphere of the coating.
  • the components self-assemble to form such a coating that the non- sticking compounds are located on top of the coating, shielding the particles, which are the adhesion sites for the sealant, from dirt.
  • sealant when sealant is applied, the sealant can reach the adhesion sites (preferably particles) and form stable bonds, in particular chemical bonds.
  • the particles are present as 0.01% to 10% by weight a colloidal suspension containing 0.01% to 60% by weight particles with a diameter up to 100 nm. In case of suspension the same solvents as used for component (d) may be used.
  • the solvent may contain mixtures of different solvents including water and aqueous solutions.
  • said solvent (d) comprises 20% to 99.9% by weight of a solvent having a dielectric constant 5 ⁇ ⁇ ⁇ 40, especially preferably a protic solvent, and 0% to 70% by weight of water.
  • the solvent preferably is a linear or branched alcohol containing 1 to 10 carbon atoms, in particular isopropanol.
  • said alkylsilane corresponding to formula (1) comprises residues R 4 conforming to the general formula (2)
  • Z is selected from the group H, Cl, and F,
  • R 1 , R 2 , and R 3 each are independently selected from Cl or cyclic, linear or branched alkoxy groups each containing 1 to 10 carbon atoms.
  • Said particle material is preferably a metal oxide and even more preferably SiO 2 .
  • the advantage of metal oxides is, that they show good compatibility with the composition system and particularly SiO 2 particles are readily available in various diameters and in water and/or in various inorganic and/or in various organic solvents. It was found that completely hydroxylated particles in a water suspension, such as in Levasil TM 200 E 20, do not solve the problem of the underlying invention exceptionally well. And when no particles are used at all, the underlying problem cannot be solved. On the other hand, when using surface modified, in particular organic surface modified particles in organic solvents, such as Highlink TM OG 502-31, the problem of the underlying invention can be solved well.
  • the protic solvent having a dielectric constant 5 ⁇ ⁇ ⁇ 40 is an alcohol, and especially preferred to be isopropanol.
  • isopropanol turned out to be the best suited solvent with optimal solvent properties and visual appearance of the coating after drying. Key criteria for judgment of visual appearance include veil formation, transparency, and clarity.
  • the acid is preferably a mineral acid, and especially preferred sulfuric acid. Sulfuric acid has the particular advantage of being non-volatile, non- oxidizing, and having a high acid strength.
  • the composition contains preferably from 0.02% to 2% by weight of at least one silane conforming to the general formula 3
  • R 4 , R 6 , R 7 , and R 8 each are independently selected from the group of Cl, oxime, and of linear and branched alkyl groups each containing 1 to 10 carbon atoms, and linear or branched alkoxy groups each containing 1 to 10 carbon atoms.
  • the silane conforming to general formula 2 is preferably selected from the group tetramethoxysilane, tetraethoxysilane, and dimethyldiethoxysilane.
  • the problem of the underlying invention is solved by a coated substrate with a hydrophobic and/or oleophobic coating containing a composition conforming to above description on at least one surface of the substrate, where the material of the substrate is selected from the group containing glass, ceramic, metal, stone, concrete and/or glazed articles.
  • the coated substrate is a glass substrate, since glass is the largest market for sealants.
  • the problem of the underlying invention is solved by a process for the preparation of said glass substrate with a hydrophobic and/or oleophobic coating comprising the steps in the following sequence:
  • the coating may be applied to the fire side and/or to the tin side of the glass substrate.
  • the composition is applied to the fire side of the glass substrate.
  • the fire side of glass substrates exhibits better adhesion to sealants.
  • the method of application in step b. is preferably selected from the group of spray coating, polishing, curtain coating, dip coating and roller coating.
  • Said composition can be applied on the whole glass pane, on the center of the glass pane and on the edges and borders of the glass pane as well.
  • Said composition allows to seal also the coated parts with common available sealants without the necessity of protecting the parts of the glass pane that should be sealed later in production. It is also not necessary to remove said coating from said parts of the glass pane before sealing, which is also common for existing coating materials.
  • adhesion sites may also be introduced by partial removal of the coating.
  • Another explanation for the positively influenced adhesion may be that loose packings of not fully crosslinked silanes are hampered by adding said nanoparticles.
  • the coating process is preferably a continuous process.
  • the process may also coat the substrates from both sides simultaneously. It should be understood that this description does not preclude chemical interactions among the components listed, but instead describes the components of a composition according to the invention in the form in which they are generally used as ingredients to prepare such a composition.
  • Highlink TM OG 502-31 an organically surface modified colloidal suspension of 30% by weight of SiO 2 particles with an average particle size of 13 nm in isopropanol by Clariant TM .
  • the surface of these particles is modified with organic residues containing alcohol functional groups, ethylenic functional groups and/or amino functional groups.
  • the degree of surface modification ranges between 2-3 per nm 2 .
  • the colloidal suspension generally contains less than 1% water by weight.
  • K ⁇ disil TM Hac-A trans Sealant for sanitary and various other applications, which is transparent.
  • Abrasion resistance was tested in analogy to ASTM D2486 using a washability tester, which was equipped with a usual mason's sponge (Triuso TM ) and a liquid containing abrasive material (Tana TM Scheuermilch, Werner & Mertz TM , DE).
  • the mass of the mount for the sponge is 345.45 g.
  • the sponge is moved about the substrate with a speed of 37 cycles/minute.
  • the result is quantified by measuring the contact angle (CA) with demineralized water before the determination of abrasion resistance and after 200, 500, 1000, 1500, 2000, ... cycles.
  • Visual appearance was determined by the human eye. Key criteria for judgment of visual appearance include veil formation, transparency, and clarity.
  • Hydrophobicity was evaluated by contact angle measurement against demineralized water in air. Unless otherwise stated, said contact angle is determined by dynamic advancing contact angle measurements using a Kruss instrument.
  • uncoated glass corresponds to measurements on the fireside of uncoated float-glass.
  • Typical hydrophobic coatings correspond to coatings as obtained by products such as Rain-X TM of Unelko as described in US 3579540 B.

Abstract

L'invention concerne un revêtement hydrophobe et/ou oléophobe facile à nettoyer appliqués sur des surfaces de verre. Ce revêtement contient des particules incrustées dans sa surface de façon que le revêtement présente une meilleure adhésion à un matériau d'étanchéité. La composition dudit revêtement comprend : a) de 0,01 % à 10 % en poids d'une suspension colloïdale contenant de 0,01 % à 60 % en poids de particules présentant un diamètre allant jusqu'à 100 nm ; b) de 0,1 % à 10 % en poids d'au moins un alkylsilane représenté par la formule générale (1) SiR1R2R3R4, dans laquelle R1, R2 et R3 représentent chacun indépendamment chlore ou un résidu organique contenant de 1 à 17 atomes de carbone, de 3 à 37 atomes d'hydrogène, de 0 à 6 atomes d'oxygène, de 0 à 33 atomes de fluor, de 0 à 33 atomes de chlore et de 0 à 5 atomes d'azote et R4 représente un résidu organique contenant de 1 à 17 atomes de carbone, de 3 à 37 atomes d'hydrogène, de 0 à 6 atomes d'oxygène, de 0 à 33 atomes de fluor, de 0 à 33 atomes de chlore et de 0 à 5 atomes d'azote ; c) de 0,05 % à 10 % en poids d'un acide ; et d) un solvant.
PCT/EP2003/014768 2003-05-28 2003-12-23 Revetement hydrophobe et/ou oleophobe pour surfaces de verre presentant des sites d'adhesion pour des materiaux d'etancheite WO2004106252A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003298231A AU2003298231A1 (en) 2003-05-28 2003-12-23 Hydrophobic and/or oleophobic coating for glass surfaces with adhesion sites for sealants

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP03400036 2003-05-28
EP03400036.4 2003-06-12

Publications (1)

Publication Number Publication Date
WO2004106252A1 true WO2004106252A1 (fr) 2004-12-09

Family

ID=33484072

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2003/014768 WO2004106252A1 (fr) 2003-05-28 2003-12-23 Revetement hydrophobe et/ou oleophobe pour surfaces de verre presentant des sites d'adhesion pour des materiaux d'etancheite

Country Status (2)

Country Link
AU (1) AU2003298231A1 (fr)
WO (1) WO2004106252A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007010955A1 (de) 2007-03-05 2008-09-11 Leibniz-Institut Für Neue Materialien Gemeinnützige Gmbh Beschichtungszusammensetzung
US8153834B2 (en) 2007-12-05 2012-04-10 E.I. Dupont De Nemours And Company Surface modified inorganic particles
WO2012167017A2 (fr) * 2011-06-01 2012-12-06 The University Of North Carolina At Chapel Hill Revêtements superhydrophobes et procédés pour leur préparation
CN110420820A (zh) * 2019-08-14 2019-11-08 杭州雅妍化妆品有限公司 一种耐刮擦玻璃瓶表面亮光喷涂工艺

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4857366A (en) * 1988-03-11 1989-08-15 Minnesota Mining And Manufacturing Company Method for obtaining adhesion of urethane sealant to a painted or glass surface
EP0545201A2 (fr) * 1991-11-29 1993-06-09 Ppg Industries, Inc. Surface en verre hydrofuge durable
DE19544912A1 (de) * 1995-12-01 1997-06-05 Gore W L & Ass Gmbh PTFE-Körper aus mikroporösem Polytetrafluorethylen mit Füllstoff und Verfahren zu dessen Herstellung
DE19719948A1 (de) * 1997-05-13 1998-11-19 Inst Neue Mat Gemein Gmbh Nanostrukturierte Formkörper und Schichten sowie Verfahren zu deren Herstellung
EP0909747A1 (fr) * 1997-10-17 1999-04-21 Erlus Baustoffwerke Ag Procédé d'obtention de surfaces auto-nettoyantes
DE19746885A1 (de) * 1997-10-23 1999-06-24 Inst Neue Mat Gemein Gmbh Nanostrukturierte Formkörper und Schichten sowie Verfahren zu deren Herstellung
DE10051182A1 (de) * 2000-10-16 2002-05-02 Nano X Gmbh Nanopartikel mit hydrophoben und oleophoben Eigenschaften, deren Verarbeitung und Verwendung
DE10063739A1 (de) * 2000-12-21 2002-06-27 Dmc2 Degussa Metals Catalysts Substrate mit selbstreinigender Oberfläche, Verfahren zu deren Herstellung und deren Verwendung

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4857366A (en) * 1988-03-11 1989-08-15 Minnesota Mining And Manufacturing Company Method for obtaining adhesion of urethane sealant to a painted or glass surface
EP0545201A2 (fr) * 1991-11-29 1993-06-09 Ppg Industries, Inc. Surface en verre hydrofuge durable
DE19544912A1 (de) * 1995-12-01 1997-06-05 Gore W L & Ass Gmbh PTFE-Körper aus mikroporösem Polytetrafluorethylen mit Füllstoff und Verfahren zu dessen Herstellung
DE19719948A1 (de) * 1997-05-13 1998-11-19 Inst Neue Mat Gemein Gmbh Nanostrukturierte Formkörper und Schichten sowie Verfahren zu deren Herstellung
EP0909747A1 (fr) * 1997-10-17 1999-04-21 Erlus Baustoffwerke Ag Procédé d'obtention de surfaces auto-nettoyantes
DE19746885A1 (de) * 1997-10-23 1999-06-24 Inst Neue Mat Gemein Gmbh Nanostrukturierte Formkörper und Schichten sowie Verfahren zu deren Herstellung
DE10051182A1 (de) * 2000-10-16 2002-05-02 Nano X Gmbh Nanopartikel mit hydrophoben und oleophoben Eigenschaften, deren Verarbeitung und Verwendung
DE10063739A1 (de) * 2000-12-21 2002-06-27 Dmc2 Degussa Metals Catalysts Substrate mit selbstreinigender Oberfläche, Verfahren zu deren Herstellung und deren Verwendung

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007010955A1 (de) 2007-03-05 2008-09-11 Leibniz-Institut Für Neue Materialien Gemeinnützige Gmbh Beschichtungszusammensetzung
US8153834B2 (en) 2007-12-05 2012-04-10 E.I. Dupont De Nemours And Company Surface modified inorganic particles
WO2012167017A2 (fr) * 2011-06-01 2012-12-06 The University Of North Carolina At Chapel Hill Revêtements superhydrophobes et procédés pour leur préparation
WO2012167017A3 (fr) * 2011-06-01 2013-03-21 The University Of North Carolina At Chapel Hill Revêtements superhydrophobes et procédés pour leur préparation
US9675994B2 (en) 2011-06-01 2017-06-13 The University Of North Carolina At Chapel Hill Superhydrophobic coatings and methods for their preparation
CN110420820A (zh) * 2019-08-14 2019-11-08 杭州雅妍化妆品有限公司 一种耐刮擦玻璃瓶表面亮光喷涂工艺

Also Published As

Publication number Publication date
AU2003298231A1 (en) 2005-01-21

Similar Documents

Publication Publication Date Title
US8822018B2 (en) Hydrophobic substrate including a plasma-activated silicon oxycarbide primer
US5464704A (en) Surface-treated substrate
US6506496B1 (en) Composition for providing a non-wettable coating, articles coated therewith, and methods for preparing the same
JP4718549B2 (ja) 自然石の封止法
CA2423657C (fr) Revetements hydrophobes a haute durabilite et procedes associes
US6156409A (en) Non-fogging article and process for the production thereof
JP2004516216A (ja) セルフクリーニング表面を有する基板、その製造方法およびその使用
EP3203273B1 (fr) Plaque de verre avec revêtement à faible réflexion, substrat de verre, et dispositif de conversion photoélectrique
KR20040052516A (ko) 피막 피복 물품, 및 이것을 이용한 기능성 피막 피복 물품
WO2008074823A1 (fr) Procédé sol-gel pour fabriquer des films protecteurs pour des substrats polymères
US20040005469A1 (en) Process for making a product with a long-lasting easily cleaned surface and product thereof
KR101996696B1 (ko) 소수성 창유리
WO1999028534A1 (fr) Procede de production d'articles recouvertes d'enrobages a base de silice
KR20000069167A (ko) 특히 창유리 시트를 위한 소수성 코팅
US20080156224A1 (en) Method of fabricating transparent hydrophobic self-cleaning coating material and coating material and transparent coating made therefrom
WO2017024383A1 (fr) Revêtements superhydrophobes de silicone élastomère
JP3427755B2 (ja) シリカ系膜被覆物品を製造する方法
KR100463926B1 (ko) 다기능성 실리콘 폴리머 코팅제 조성물
TWI784014B (zh) 組成物以及將其硬化而成的膜
JP2004137137A (ja) 皮膜被覆物品、その製造方法、およびそれに用いる塗布溶液
WO2004106252A1 (fr) Revetement hydrophobe et/ou oleophobe pour surfaces de verre presentant des sites d'adhesion pour des materiaux d'etancheite
CA2558420C (fr) Verre architectural revetu de silicone
CN110358445B (zh) 拒水膜形成用组合物和拒水膜
EP3359606B1 (fr) Revêtement antireflet hautement durable durcissant à température ambiante contenant des nanoparticules
JP2000336334A (ja) シリカ系膜被覆物品および機能性膜被覆物品を製造する方法

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): BW GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP